US2025011177A1PendingUtilityA1

Use of 1-methyl-6,7-dihydro-5h-cyclopenta[b]pyridine-1-ium cation as structure directing agent for the preparation of zeolites and zeolites obtained using the same

Assignee: EXXONMOBIL TECHNOLOGY & ENGINEERING COMPANYPriority: Jun 18, 2021Filed: Jun 8, 2022Published: Jan 9, 2025
Est. expiryJun 18, 2041(~14.9 yrs left)· nominal 20-yr term from priority
C07D 221/04C01P 2004/03C01P 2002/72C01B 39/12B01J 37/105B01J 37/04B01J 37/031B01J 37/0018B01J 29/86B01J 29/70B01J 29/035C01B 39/06C01B 39/48C10G 49/08C10G 11/05C01B 37/02
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Claims

Abstract

This disclosure relates to the use of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-ium cation as structure directing agent (SDA) for the preparation of zeolites. This disclosure also relates to compositions of matter, designated as EMM-64 and EMM-65, obtainably by using this SDA, as well as a method of making the same and uses thereof. This disclosure further relates to a method of making an aluminosilicate molecular sieve of RTH framework type using said SDA, aluminosilicate molecular sieves of RTH framework type obtainable by said method, and uses thereof.

Claims

exact text as granted — not AI-modified
1 - 23 . (canceled) 
     
     
         24 . Use of 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-ium cation of Formula I: 
       
         
           
           
               
               
           
         
         as a structure directing agent for the preparation of zeolites. 
       
     
     
         25 . The use of  claim 24 , wherein the 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-ium cation of Formula I is in its hydroxide and/or halide form. 
     
     
         26 . The use of  claim 24 , for the preparation of EMM-64, EMM-65 or aluminosilicate RTH framework type zeolite. 
     
     
         27 . A crystalline material designated EMM-64, having, in its as-calcined form, an X-ray diffraction pattern including at least 9 of the peaks selected from Table 1: 
       
         
           
                 
                 
                 
               
                     
                   TABLE 1 
                 
                     
                     
                 
                     
                   degree 2-theta 
                   relative intensity 
                 
                     
                   (±0.20) 
                   [100 × I/(Io)] 
                 
                     
                     
                 
                     
                 
                 
                 
                 
               
                     
                   8.11 
                    60-100 
                 
                     
                   9.10 
                   10-20 
                 
                     
                   12.86 
                   10-20 
                 
                     
                   13.41 
                   10-30 
                 
                     
                   15.20 
                   30-60 
                 
                     
                   19.74 
                   20-40 
                 
                     
                   19.94 
                   10-30 
                 
                     
                   20.65 
                   40-70 
                 
                     
                   23.78 
                   40-70 
                 
                     
                   27.11 
                   10-20 
                 
                     
                   27.70 
                   10-30 
                 
                     
                   28.70 
                   10-30 
                 
                     
                     
                 
             
                
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         28 . The material of  claim 27 , having an X-ray diffraction pattern including all the peaks selected from Table 1. 
     
     
         29 . The material of  claim 27  having a molecular formula of Formula II:
   (m)X 2 O 3 :YO 2    (Formula II),
 
 wherein 0≤m≤0.025, X is a trivalent element, and Y is a tetravalent element; wherein X includes one or more of Al, B, Fe and Ga, and Y includes one or more of Si, Ge, Sn, Ti and Zr. 
 
     
     
         30 . The material of  claim 29 , wherein X comprises or is Al and/or B, and Y comprises or is Si. 
     
     
         31 . A crystalline material designated EMM-64, having, in its as-synthesized form, an X-ray diffraction pattern including at least 7 of the peaks selected from Table 3: 
       
         
           
                 
                 
                 
               
                     
                   TABLE 3 
                 
                     
                     
                 
                     
                   degree 2-theta 
                   relative intensity 
                 
                     
                   (±0.20) 
                   [100 × I/(Io)] 
                 
                     
                     
                 
                     
                 
                 
                 
                 
               
                     
                   8.08 
                   20-40 
                 
                     
                   15.20 
                   10-30 
                 
                     
                   19.54 
                   30-60 
                 
                     
                   19.94 
                   10-30 
                 
                     
                   20.56 
                   50-80 
                 
                     
                   23.79 
                    60-100 
                 
                     
                   27.12 
                   10-30 
                 
                     
                   27.69 
                   20-40 
                 
                     
                   28.50 
                   20-40 
                 
                     
                     
                 
             
                
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         32 . The material of  claim 31 , having an X-ray diffraction pattern including all the peaks selected from Table 3. 
     
     
         33 . The material of  claim 31  having a molecular formula of Formula III:
   (n)Q:(m)X 2 O 3 :YO 2    (Formula III),
 
 wherein 0≤n≤0.2, 0≤m≤0.025, Q is 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-ium cation of Formula I, X is a trivalent element, and Y is a tetravalent element, 
 
       
         
           
           
               
               
           
         
         wherein X includes one or more of Al, B, Fe and Ga, and Y includes one or more of Si, Ge, Sn, Ti and Zr. 
       
     
     
         34 . The material of  claim 33 , wherein X comprises or is Al and/or B, and Y comprises or is Si. 
     
     
         35 . The crystalline material of  claim 27 , having a framework defined by the following connectivities in Table 2 for the tetrahedral (T) atoms in the unit cell, the tetrahedral (T) atoms being connected by bridging atoms: 
       
         
           
                 
                 
               
                   TABLE 2 
                 
                     
                 
                   Topol. equiv. 
                     
                 
                   T-atom a   
                   Coordination Sequence N 1  to N 12   
                 
                     
                 
                     
                 
                 
                 
                 
                 
                 
                 
                 
                 
                 
                 
                 
                 
                 
               
                   T1 
                   4 
                   11 
                   24 
                   39 
                   66 
                   98 
                   129 
                   162 
                   209 
                   263 
                   327 
                   385 
                 
                   T2 
                   4 
                   12 
                   24 
                   42 
                   67 
                   83 
                   128 
                   171 
                   217 
                   262 
                   322 
                   385 
                 
                   T3 
                   4 
                   12 
                   25 
                   41 
                   64 
                   95 
                   132 
                   168 
                   209 
                   265 
                   330 
                   384 
                 
                   T4 
                   4 
                   11 
                   23 
                   42 
                   67 
                   94 
                   126 
                   167 
                   213 
                   265 
                   317 
                   380 
                 
                     
                 
                     a Topologically equivalent atom positions have the same “T-type” symbol. 
                 
                     b  Size and number of smallest ring on each angle of the T-atom (M. O'Keeffe and S. T. Hyde,  Zeolites , 19, 370 (1997)). 
                 
             
                
                
                
                
                
               
               
                
               
            
             
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         36 . A method for preparing the EMM-64 crystalline material of  claim 27 , comprising:
 (a) preparing a synthesis mixture comprising water, a source of an oxide of tetravalent element (Y), optionally a source of an oxide of trivalent element (X), a structure directing agent (Q), a source of fluoride ions (F), optionally a source of hydroxide ions (OH), and optionally a source of alkali and/or alkaline earth metal element (M),   wherein the structure directing agent (Q) comprises 1-methyl-6,7-dihydro-5H-cyclopenta[b]pyridine-1-ium cation of Formula I:   
       
         
           
           
               
               
           
         
       
       and
 wherein the synthesis mixture comprises fluoride ions (F) in a F/Y molar ratio of at least 0.1; 
 (b) heating said synthesis mixture under crystallization conditions including a temperature of from 100° C. to 200° C. for a time sufficient to form crystals of said crystalline material; 
 (c) recovering at least a portion of the crystalline material from step (b); and 
 (d) treating the crystalline material recovered in step (c) to remove at least part of the structure directing agent (Q). 
 
     
     
         37 . The method of  claim 36 , wherein the synthesis mixture has the following composition in terms of molar ratios: 
       
         
           
                 
                 
                 
                 
               
                     
                 
                   Molar ratios 
                   Typical range 
                   Preferred range 
                   More preferred range 
                 
                     
                 
                   Y/X 
                       10-infinity 
                   20-500 
                   20-100 
                 
                     
                     
                   (if X present) 
                   (if X present) 
                 
                   Q/Y 
                   0.01-1.0   
                   0.05-1.0 
                   0.1-0.8 
                 
                   F/Y 
                   0.1-1.0     
                    0.2-0.8 
                   0.3-0.7 
                 
                   OH/Y 
                   0-1.5 
                   0.05-1.0 
                   0.1-0.8 
                 
                     
                     
                   (if OH present) 
                   (if OH present) 
                 
                   M/Y 
                   0-1.5 
                   0.05-1.0 
                   0.1-0.8 
                 
                     
                     
                   (if M present) 
                   (if M present) 
                 
                   H 2 O/Y 
                    1-100 
                    1-75 
                    1-50 
                 
                     
                 
             
                
                
                
               
               
                
                
                
                
                
                
                
                
                
                
               
            
           
         
       
     
     
         38 . A process of converting an organic compound to a conversion product comprises contacting the organic compound with the crystalline material of  claim 27 .

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